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The term is used in a number of contexts, but its primary aim is to be derogatory towards the male in the conversation with a secondary goal of attacking the female.

The use of the term that is perhaps most closely tied to the trope of a "white knight" supposes that the woman is perfectly capable of defending herself, and that by "coming to her rescue" the knight is undermining her, which is counterproductive to the woman gaining any sort of respect. While sometimes appropriate, this is often misused as a thought-terminating cliché, for example to attack any man expressing concerns about sexism.

Another use of the term suggests that the male intends to curry favor with the woman in order to seduce her—irrespective of whether this is actually true. It's a byproduct of the dickwad theory as applied to sexism, used as an attempt to shame defenders of a woman into backing off. This allows the hecklers to harass her by implying that the defenders must have an ulterior motive. When successful, it can be considered a form of heckler's veto. Either that, or it is just simply used as a method of attacking the person making an argument rather than their actual arguments.

When this kind of behavior is actually done for real, it's usually perceived as creepy, manipulative-bordering-on-stalking Nice Guy™ behavior and is almost always unwelcome, making the perceived sting of the accusation worse. However, even in the unlikely scenario that seducing the female really is the male's intention, it still would not automatically make him wrong.

When the woman being defended does not conform to mainstream standards of beauty, so that it seems incomprehensible why someone would want to seduce her, an alternative explanation put forth is that the defender lacks experience with women and therefore naively idealizes them. Both kinds of ad hominem arguments focus on the defender's alleged romantic failings.[1]

Accusations of being a white knight are very Godwin's Law-esque; if any guy speaks out against sexism directed towards women on the internet, it is inevitable that somebody will accuse him of being one.